THE  STRUCTURE  OF  THE  MERCURY 
DERIVATIVES  OF  THE  OLEFINES 


BT 


WARREN  M.RON  SPERRY 

B.  Chern.,  Corneil  University,  1921 


THESIS 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF  MASTER  OF  SCIENCE  IN  CHEMISTRY 
IN  THE  GRADUATE  SCHOOL  OF  THE  UNIVERSITY 
OF  ILLINOIS.  1922 


l.’RBANA.  ILLINOIS 


!2^SpZ2  -i  ^ P 


/922 
Sf>  3 7 

UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


. July  29  ^192  2 

I HEREBY  RECOMMEN13  THAI'  THE  THESIS  PREPARED  UNDER  MY 

SUPERVISION  BY_  WARREN  MYRON  SPERRY 

ENTITLED  THE  STRUCTURE  OF  THE  MERCURY-DERIVATIVES 


OF  ^THE  OLEFINES . 

BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 
THE  DEGREE  OF  MASTER  OF  SCIENCE 


Recommendation  concurred  in* 


Committee 

on 


Final  Examination* 


Required  for  doctor’s  degree  but  not  for  master's 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/structureofmercuOOsper 


ACKNOWLEDGMENT 


The  author  wishes  to  acknowledge  his  Indebtedness  to 
Professor  Roger  Adams  for  suggesting  the  subject  of  this 
research  and  for  his  many  helpful  suggestions  throu^out 
the  work* 


CONTENTS 


Page 

I.  INTRODUCTION 1 

II.  HISTORICAL  AND  THEORETICAL 2 

A.  The  Structiiral  Theory  of  Sand 2 

1.  Arguments  Against 3 

2.  Arguments  in  Favor 4 

B.  cx-Mercurochloro  Methyl  Coumarane 4 

1.  Significance  of  Structure 4 

2.  Proof  of  Struct\u?0 5 

a.  Analysis 5 

b.  Poi*mation  in  Absolute  Alcohol 5 

c.  Action  with  Sodium  Amalgam 6 

d.  Rate  of  Decomposition 6 

III.  EXPERIMENTAL 8 

A#  o-Allyl  Phenol 8 

B.  c?c -Mercurochloro  Methyl  Coumarane 8 

1.  Formation  in  Water 8 

2.  Analysis  for  Mercury.... 9 

3.  Formation  in  Absolute  Ethyl  A.lcohol 11 

4*  Formation  in  Butyl  Alcohol 13 

C.  OC -MercTiroiode  Methyl  Coumarane 13 

D.  Mercuric  Acetate  Derivative  of  o-Allyl  Anisole . . 14 

E.  Mercuric  Chloride  Derivative  of  o-Allyl 18 

Anisole 

P.  The  Time  of  Decomposition 19 

IV.  CONCLUSION 21 

V.  SUMMARY 22 

VI.  BIBLIOGRAPHY 23 


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THE  STRUCTURE  OP  THE  MERCURY  DERIVATIVES 
OF  THE  OLEFINES. 

I.  INTRODUCTION. 

It  has  been  well-known  for  over  twenty  years  that  Inorganic  mer- 
cury salts  react  with  ethylene,  and,  as  far  as  is  known,  v/ith  all  of 
the  olefines  of  the  ethylene  type,  usually  in  alkaline  solution,  to 
form  compounds  of  the  type  RHgXOH  or  (RH^)20.  Although  most  of 
these  compounds  are  very  well  crystallized,  easily  formed,  and  easy 
to  handle,  and  although  they  have  been  quite  thoroughly  investigated, 
there  is  still  considerable  question  as  to  their  correct  structxu?e. 

This  work  was  taken  up  with  the  idea  that  a study  of  the  mercury 
derivative,  analogous  to  the  types  mentioned  above,  of  such  compounds 
as  o-allyl  phenol  might  shed  light  on  the  correct  structure.  The 
reasons  for  arriving  at  this  conclusion  will  appear  under  the  dis- 
cussion of  theory. 


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II.  HISTORICAL  AND  THEORETICAL. 

It  was  first  discovered  by  Deniges^  that  the  olefines  generally, 
with  the  exception  of  ethylene,  combine  with  merc\iric  sulphate  in 
acid  solution  and  yield  yellow  compounds  of  the  type  (SO^Hg,  HgO)sR, 
in  which  R is  an  olefine.  He  found  that  these  compounds  dissolve 
readily  in  HCl  with  effervescence  of  the  particular  olefine  gas  from 
which  the  compound  was  derived. 

Hofman  and  Sand^  studied  this  general  reaction  in  more  detail 
and  found  that  the  following  types  of  compounds  were  formed  by  the 
action  of  ethylene  on  solutions  of  mercuric  salts:  (1)  Ethanol  mer- 
cury salts  of  the  form  OH  - CHg  - CHg  - HgJC;  (2)  ethyl  ether  mercury 
salts  of  the  form  0(CH2  - CHa*H^)2.  They  explained  the  formation 
of  these  compounds  on  the  supposition  that  the  mercury  salt  HgXa 
splits  into  the  ions  HgpC  and  X which  then  combine  with  the  ethylene, 
converting  it  into  the  saturated  compound  XHg  - CHa  - CHa  - X which 
then  undergoes  hydrolysis  to  form  the  ethanol  mercury  compound. 
Compounds  of  the  second  type  migjit  result  from  the  following  reac- 
tion, XHg  - CHa  - CHa  - - CHg  - HgX  = 0(CHa.CHa.HgX)a 

+ HX.  These  investigators  also  reported  compounds  of  the  type 
CHa  = CH  - HgX  and  (CaHaHgX)^^  but  they  seem  to  have  later  abandoned 
the  view  that  such  compounds  existed.  It  is  now  knoAvn  that  the  com- 
pounds studied  and  reported  to  be  these  were  identical  with  the 
ethanol  compounds. 

Later  investigators,  particularly  Manchot®  doubt  the  structure  I 
of  these  compounds  as  proposed  by  Hofman  and  Sand.  He  bases  his  dls- 


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agreeraent  on  the  fact  that  practically  all  of  these  compounds  are 
very  easily  and  rapidly  decomposed  by  HCl*  Sand^  explains  this  re- 
action by  assuming  that  it  occurs  in  the  following  steps:  (1)  Re- 
placement of  the  hydroxyl  group  by  Cl,  and  (2)  the  splitting  out  of 
HgCla*  Manchot®  says  that  this  mechamism  is  untenable  because  no 
case  is  known  of  an  alcoholic  hydroxyl  being  so  easily  and  readily 
replaced  by  a Cl,  and,  moreover,  no  case  is  known  of  a Cl  splitting 
out  of  the  group  -CHaCl  without  difficulty.  But  these  compounds  de- 
compose almost  instantly;  so  rapidly  in  fact  that  from  the  ethylene 
addition  compounds,  ethylene  is  evolved  with  almost  the  speed  with 
which  CO2  is  evolved  from  a carbonate  upon  the  addition  of  acid. 


Sand®  also  proposed  another  possible  explanation  of  the  mechan- 
ism of  this  decomposition.  This  depends  on  the  possibility  of  two 
tautomeric  forms. 

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CHa  - CHa  ^ XHgCHa  - CHaOH 

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According  to  this  theory  the  effect  of  acid  is  to  drive  the 
above  reaction  to  the  left  with  the  formation  of  form  I from  which 
ethylene  is  readily  split  off.  Manchot  considers  this  theory  to  be 
untenable  because  (1)  it  is  \inthinkable  that  full  valence  will 
change  to  a partial  valence,  (2)  it  is  difficult  to  conceive  of  an 
hydroxyl  group  leaving  the  stable  alcohol  grouping  and  migrating  to 
a mercury  atom  merely  on  the  addition  of  weak  HCl,  and  (3)  this 
theory  does  not  explain  the  action  on  compounds  of  the  type 
(XHg  - CHa  - CHa)20. 


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The  question  then  is  whether  these  compounds  have  a definite 
structural  form,  or  whether  they  are  merely  molecular  addition  com- 
pounds without  definite  structural  formulas*  The  argximents  in  favor 
of  the  structural  formulas  are  as  follows:  (1)  The  ethanol  mercuric 
iodide  reacts  with  iodine  dissolved  in  potassium  iodide  to  give 
ethylene  iodohydrine  and  under  the  same  conditions  the  diethyl  ether 
dlmercuric  iodide  gives  (S  (3  diiodo  - diethyl  ether;  (2)  many  of 
these  compounds  when  treated  with  sulphides  yield  the  corresponding 
alcohols  according  this  general  reaction 

OH  - C - C - + HaS  HO  - S - fi  - H + HgS  + HX 

As  an  example  may  he  given  the  reaction  with  the  derivatives  of  cin- 
namic acid’’’* 

CqHs  - CH  - OH  - COgR^  + NH3  + HaS  ^ CeHg  - GH  - CHg  - COgR^ 


Such  reactions  as  these  it  is  almost  impossible  to  explain  on  the 
basis  of  a molecular  structure* 

This  work  was  taken  up  in  an  endeavor  to  furnish  further  evi- 
dence in  favor  of  the  theory  of  the  structure  of  these  compounds  as 
proposed  by  Sand.  It  was  thought  that  a study  of  the  structure  of 
the  mercury  addition  product  of  o-allyl  phenol  migjit  furnish  such 
evidence  because  if  the  Sand  theory  is  true,  the  compound  as  first 
formed  would  have  this  struct\ire 


and  it  would  be  very  likely  that  water  would  split  out  from  the  ad- 


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In  case  such  a compound  should  be  formed,  it  would  be  an  almost  in- 
contestable proof  that  at  least  this  particular  addition  product  conJ 
formed  to  Sand's  theory* 

The  mercuric  chloride  addition  product  of  o-allyl  phenol  was 
made  and  it  was  found  that  it  was,  as  predicted,  a coumarane  deriva- 

I 

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tive  of  the  structure  indicated  above*  This  structvire  was  proved  by 
the  following  points:  (a)  The  analysis  of  three  constituents  checked 
the  theoretical  for  this  structure;  (b)  the  compound  was  made  in  ab- 
solute ethyl  and  absolute  butyl  alcohol  solutions;  (c)  upon  treatment 
with  sodium  amalgam  a compound  was  formed  which  gave  a correct  analy- 
sis for  this  structure®; 


(d)  this  compound  formed  readily  in  acid  solution  and  was  not  rapidly 
decomposed  by  HCl*  j 

I 

The  fact  that  a compound  was  obtained  in  absolute  alcohol  solu- 
tion identical  with  the  one  obtained  from  water  solution  is  almost  a 
final  proof  of  the  ring  structure  since  in  all  other  olefine  addition 
compounds  an  -OR  compound  is  formed  where  ROH  is  the  alcohol  em- 
ployed as  solvent* 

CHa  = CHg  + HgCla  + ROH ^ RO  - CHa  - CHa  - HgCl  + HCl 


The  only  possible  explanation  of  this  reaction  is  the  following: 


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The  action  of  sodium  amalgam  in  forming  RgHg  compounds  is  fairly 
general. 

2RHgX  + sodium  amalgam  RgHg  + HgXa 

Therefore,  when  a compound  is  obtained  which  gives  the  correct 
analysis  for  the  one  vs^ich  would  be  obtained  if  the  coumarane  struc- 
ture is  correct  and  the  general  reaction  occurs,  it  is  fairly  good 
evidence  in  favor  of  the  coumarane  structure.  Moreover,  it  is  very 
difficult  to  find  a molecular  formula  which  will  satisfy  the  analy- 
sis of  the  compound. 

A fairly  extended  study  of  the  speed  of  solution  of  this  corapo\ind 
in  various  strengths  of  HCl  and  HC2H3O3  was  made  since  its  behavior 
in  this  connection  appeared  to  be  very  significant.  Sand^  directs 
that  these  olefl.ne  derivatives  be  made  in  a weakly  alkaline  solution. 
They  do  not  form  in  acid  solution  because  acid  decomposes  them  as 
fast  as  they  are  formed.  The  equilibrium  may  be  expressed  as  fol- 
lows: 

CHg  = CHs  + HgCla  ClCHg  - CHa  - HgCl 

n 

OH  - CHa  - CHa  - HgCl  + HCl 

Assuming  as  we  must  that  these  are  reversible  reactions  the  presence 
of  an  excess  of  HCl  would  force  them  both  to  the  left  to  give  ethy- 
lene and  mercuric  chloride. 


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It  was  found,  however,  that  the  mercuric  chloride  derivative  of 
o-allyl  phenol  formed  almost  instantly  in  the  cold  with  fairly  high 
yields  in  acid  solution  while  the  mercuric  chloride  derivative  of 
o-allyl  anisole  did  not  form  at  all  in  acid  solution  and  only  very 
slowly  if  at  all  in  alkaline  solution* 

The  time  of  decomposition  of  the  mercuric  chloride  derivative  of 
o-allyl  phenol  was  taken  for  various  concentrations  of  acid  as  given 
in  the  table  under  experimental.  This  table  shows  clearly  that  the 
decomposition  is  relatively  slow.  In  the  case  of  practically  all  of 
these  olefine  mercury  compounds  it  is  almost  instantaneous.  The  mer- 
curic acetate  derivative  of  o-allyl  anisole  was  made  and  although  it 
is  a syrupy  compound  very  difficult  to  purify,  it  was  observed  that 
it  decomposed  almost  Instantly  with  strong  HCl  to  give  o-allyl  ani- 
sole and  mercuric  salts. 


These  phenonoma  may  be  explained  by  a series  of  equilibria  as 
follows: 

(2) 

H (1)  Cl  +H2O  JM jpHj 

CH8-CH=CH2+HgCl2  ^\-CH2-CH-CH2-HgCl  \,CH2-CH-CH2-HgCl 


1|(3) 

I^^^^CH^CH-CHa-HgCl+HzO 


Equilibria  (1)  and  (2)  are  the  general  equilibria  for  all  these  com- 
pounds; but  equilibria  (3)  tends  to  throw  the  whole  reaction  to  the 
right  and  counteract  the  reversing  action  of  the  HCl.  This  equili- 
brium probably  tends  to  go  rather  strongly  to  the  right  and  so  the 
compound  is  formed  in  acid  solution  and  acid  dissolves  it  slowly* 


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8 


III.  EXPERIMENTAL. 

0-Allyl  Phenol. 

I 

This  compound  was  made  by  the  rearrangement  of  allyl  phenyl 
ether,  according  to  the  general  directions  of  Claisen®  with  the  modi- 
fications given  by  Adams  and  Rlndfusz^®. 

oc-Mercurochloro  Methyl  Coumarane . 

To  a sli^tly  acid  solution  of  22  g.  mercuric  chloride  in  250  cc. 
of  water  were  added  slowly  with  vigorous  stirring  10  g.  of  o-allyl 
phenol.  A white  solid  commenced  to  precipitate  at  once.  The  mix- 
ture was  allowed  to  stand  over  ni^t  and  was  then  filtered  and 

o 

washed  well  with  water.  It  was  dried  and  recrystallized  from  95 

ethyl  alcohol.  The  melting  point  of  the  recrystallized  product  was 

e 

137.5  • A small  amount  was  recrystallized  from  fresh  alcohol  and 
the  same  melting  point  was  obtained,  so  the  compound  was  taken  as 
pure.  The  recrystallized  compound  is  formed  in  beautiful,  shiny, 

flaky  crystals.  The  yield  of  the  recrystallized  product  (without 

o 

concentration  of  mother  liquors)  was  18.5  g.  this  being  a 67.3  /® 
yield.  This  yield  ml^t  have  been  increased  by  using  a larger  ex- 
cess of  mercuric  chloride  and  by  the  slower  addition  of  the  phenol.  1 
At  any  rate  it  is  a largo  yield  for  a mercury  addition  in  acid  solu-  [ 
tion.  A theoretical  yield  would  not  be  expected  because  there  is 
undoubtedly  an  equilibrium  set  up  as  is  shown  by  the  solubility 


table  below 


9 


The  compound  was  analyzed  for  carbon  by  the  peroxide  bomb  method 
with  the  following  results: 


II 


III 


Wt.  of  sample 
( grams ) 

.5355 

• • • • 

.6243 

7794 

Vol.  of  Cla 
(cc. ) 

344.8 

# • • • 

396.2 

493.8 

Barometer 
(mm.  of  Hg) 

743 

• • « • 

743 

....  743 

Temperature 

30® 

• # « • 

28® 

....  26.2® 

o 

o 

o 

29.10 

• • • • 

29.01 

....  29 . 23 

Theoretical  for 

■GHg^^CH 

- CHs  - 

HgCl  29.26 

The  compound  was 

analyzed  for  chlorine  by 

the  Carius  meth< 

following  results 

• 

• 

I 

II 

Wt . of  sample 

.2853 

• • # • 

.3231 

Wt.  AgCl 

.1116 

# « • • 

.1268 

“/o  Cl 

9.68 

• « • e 

9.708 

Theoretical  forf^^cST^H-CHs-HgCl  9.62 


Considerable  difficulty  was  encountered  in  the  analysis  for  mer- 
cury. The  following  set  of  directions  was  finally  worked  out  and 
used  in  the  analyses. 

A sample  of  about  .5  g.  is  welded  into  a 200  cc.  round  bottom 
flask  which  is  fitted  with  a tight  stopper  carrying  a dropping 
funnel  and  a bent  glass  tube  leading  to  a Plllgot  tube.  This  appa- 
ratus is  described  by  Bauer in  his  description  of  a somewhat  slmi- 


tv:  MFumuiu  I 


<1 


r 


' . . . V. 


.} 


- I'  V 


o 


10 


lar  method  of  analysis.  It  might  be  stated  that  Bauers*  method  was 
tried  and  might  have  worked  had  the  hydrogen  peroxide  used  been 
strong  enough.  At  any  rate  check  results  could  not  be  obtained 
using  this  method.  To  the  sample  are  added  3 cc.  concentrated  HCl 
throu^  the  dropping  funnel  and  the  mixture  is  boiled  until  complete 
solution  has  taken  place.  It  is  then  diluted  to  100  cc.  and  in  the 
same  flask  the  mercury  is  precipitated  as  the  sulphide.  This  is 
filtered  and  well  washed  and  the  filter  paper  containing  the  sul- 
phide is  transferred  to  the  same  flask  and  connected  to  the  same  ap- 
paratus described  above.  The  Pillgot  tube  v/hich  contains  any  mer- 
cury which  may  have  distilled  out  during  the  solution  process  is  not 
disturbed  during  the  precipitation  or  filtration  processes.  The 
sulphide  is  now  dissolved  in  about  3-4  cc.  of  aqua  regia  and  after 
dilution  the  solution  is  filtered  to  remove  paper  and  sulphur  and 
then  made  ammoniacal.  To  this  ansnoniacal  solution  are  added  5 cc. 
of  10®/®  potassium  iodide  solution  and  then  1 cc.  of  a standard  sil- 
ver nitrate  solution.  This  gives  a white  precipitate  of  Agl. 
Standard  potassium  cyanide  solution  is  then  added  until  the  precipi- 
tate just  dissolves.  In  usual  procedure  as  the  end-point  is  some- 
what hard  to  detect  at  the  first  trial  it  is  best  to  back-tltrate 
adding  more  silver  nitrate  from  a burette  and  finally  subtracting 
the  silver  nitrate  \ised  in  the  terms  of  its  equivalent  in  potassium 
cyanide.  This  method  of  titration  was  the  same  as  that  used  by 
Bauer  except  for  the  fact  that  it  was  found  better  to  use  more  in- 
dicator than  he  used.  Some  trouble  was  encountered  from  the  fact 
that  a deep  yellow  color  usually  appeared,  when  the  solution  was 
made  ammoniacal,  which  interfered  somewhat  with  the  end-point.  With 


i;  0 


j.-} 


• • r ■ *> 


r 


>•. 


11 

practice  a good  end-point  may  be  obtained,  however,  in  the  presence 
of  this  color.  A black  background  is  best  for  this  end-point.  It 
was  fo\ind  best  to  use  fairly  weak  solutions  (.02-. 03  N)  because  with 
the  more  concentrated  solutions,  which  were  used  at  first,  so  little 
solution  was  used  for  the  sample,  taken  that  no  checks  could  be  ob- 
tained. The  silver  nitrate  solution  was  standardized  by  the  silver 
chloride  gravimetric  method  using  Gooch  crucible.  The  potassium 
cyanide  solution  was  standardized  by  running  the  ratio  with  the  sil- 
ver nitrate  by  the  same  titration  method  used  in  the  analysis.  The 


following  data  were 

obtained  from  the 

analyses. 

Wt.  of  sample 

I 

. 5203  .... 

II 

. 4298  .... 

III 

.5940 

Vol.  NaCN  sol. 
equivalent  to 
the  mercury 

51.19  .... 

45 . 50  .... 

58.32 

Normality  fac- 
tor of  NaCN 
sol. 

.02757  .... 

.02757  .... 

.02757 

®/^  Mercury 

54 . 42  .... 

54 . 07  .... 

54.30 

Theoretical  for 

CH  - 

CHs  - HgCl 

54.27 

This  compound  was  also  analyzed  for  mercury  by  Professor  Whit- 
more, of  Northwestern  University,  by  his  gold  crucible  method^®  and 
the  results  agreed  very  closely  with  those  obtained  above. 

Reaction  of  Mercxxric  Chloride  and  o-Allyl  Phenol 
in  Absolute  Alcohol. 

To  a solution  of  13.5  g.  mercuric  chloride  in  43  cc.  absolute 
alcohol  were  added  6 g.  o-allyl  phenol.  A white  precipitate  com- 
menced to  form  as  soon  as  stirring  was  started.  At  the  end  of 


\ 


>i^- 


i . 


! 


/ 


r y 


h 

ii 


I 

?i 


» . 


t 


*1 


ttAl 


12 


twenty  minutes  stirring  this  was  filtered  and  dried.  The  melting 
point  was  136®  and  the  yield  4.5  g.  On  recrystallization  from 
110  cc.  95®/o  alcohol  3.8  g.  of  product  melting  at  137.5®  were  ob- 
tained . 

Fifteen  grams  of  mercuric  chloride  were  added  to  the  filtrate 
slowly  (as  fast  as  it  dissolved).  A white  precipitate  commenced  to 
form  and  a large  amount  came  down.  This  was  filtered  and  melted  at 
134®  and  the  yield  was  15  g.  On  recrystallization  from  250  cc.  al- 
cohol 5.5  g.  melting  at  137.5®  were  obtained. 

The  solution  was  again  saturated  with  mercuric  chloride  and  al- 
lowed to  stand  over  night.  A small  amount  of  precipitate  had  formed 
and  was  filtered  but  did  not  melt  up  to  145®  and  so  was  discarded. 

The  alcohol  resid^aes  from  the  recrystallizations  were  concen- 
trated and  on  the  addition  of  water  a white  silvery  precipitate  of 
the  appearance  of  calomel  appeared.  This  was  filtered  but  did  not 
melt.  There  was  tendancy  for  these  solutions  to  become  red  in  color. 

Some  of  the  recrystallized  product  obtained  above  was  mixed  with 
cx:  -mercurochloro  methyl  coumarane  sind  the  same  melting  point  137.5® 
was  obtained.  Prom  this  we  may  conclude  that  a 56®/o  yield  of  pure 
oc  -mercurochloro  methyl  coumarane  is  obtained  in  a saturated  abso- 
lute alcohol  solution  of  merc\iric  chloride  and  that  there  is  some 
evidence  of  the  partial  oxidation  of  the  phenol  with  the  formation 
of  calomel. 


‘ J>1C  'J 


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13 

Reaction  of  Mercuric  Chloride  with 
o-Allyl  Phenol  In  Butyl  Alcohol  Solution. 

To  a solution  of  9 g.  mercuric  chloride  in  41  g.  absolute  n-buty] 
alcohol  were  added  4.3  g.  o-allyl  phenol.  In  about  five  minutes  a 
white  precipitate  commenced  to  form  and  came  down  in  fairly  large 
amounts.  This  was  filtered  and  recrystallized  giving  a yield  of 
2.3  g.  of  a white,  crystalline  product  melting  at  137.5®  and  giving 
the  same  melting  point  when  mixed  with  c?c  -mercurochloro  methyl 
coumarane . 

cac "Merciaroiodo  Methyl  Coumarane. 

To  a solution  of  10  g.  of  potassium  iodide  in  200  cc.  of  water 
were  added  10  g.  oc -mercurochloro  methyl  coumarane.  This  mixtxire 
was  vigorously  stirred  and  heated.  At  about  80®  the  crystals  ap- 
peared to  become  more  amorphous.  The  heating  was  continued  just  to 
the  boiling  point  and  stirring  was  continued  until  the  mixture  cooled 
The  solid  was  filtered  and  washed  well  with  water  and  dried.  The 
yield  at  this  point  was  13.4  g.  of  crystals  melting  at  115®-116®. 

The  theoretical  yield  is  only  12.5  g.  and  probably  the  excess  yield 
was  due  to  occlusion  of  water  or  error  in  the  balance.  This  product 
was  recrystallized  using  250  cc.  of  95®/^  alcohol.  This  time  10  g. 
of  shiny  white  plates  were  obtained  which  became  grayish  on  standing. 
The  melting  point  was  115. 5®- 116. 5® . On  a second  recrystallization 
using  170  cc.  of  alcohol  8 g.  of  beautiful,  white,  shiny  crystals 
were  obtained  melting  at  116®-116.5®. 


_r 


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r 


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r r ..  r 


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j. 


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14 


This  compound  was  analyzed  by  Professor  ¥/hitmore  for  mercury  and 
the  results  obtained  checked  closely  with  the  theoretical  for 

^.CHa^CH  - CHg  - Hgl 

o-Allyl  Anlsole. 

o-Allyl  anisole  was  made  by  the  directions  given  by  Adams  and 
Rindfusz^® . 

The  Mercuric  Acetate  Derivative  of 
0"Allyl  Anisole » 

13 

Following  the  directions  given  by  Balbiano  and  Paolini  for 
making  the  mercuric  acetate  derivative  of  aplol,  an  attempt  was  made 
to  make  the  corresponding  derivative  of  o-allyl  anisole*  To  a solu- 
tion of  3.18  g*  HgCCgHaOg)  in  12.5  cc.  water  were  added  1.5  g. 
o-allyl  phenol  with  stirring.  It  was  noted  that  in  about  fifteen 
minutes  the  oil  which  floated  at  first  was  commencing  to  settle  to 
the  bottom  and  become  very  syrupy  and  stringy.  Some  of  this  syrup 
was  washed  as  well  as  possible  with  water  and  then  boiled  a short 
time  with  concentrated  HCl.  o-Allyl  anisole  and  a solution  from 
which  mercuric  sulphide  was  precipitated  in  large  quantities  by  HgS, 
were  obtained.  The  o-allyl  anisole  was  identified  by  extraction 
with  ether  and  determination  of  the  boiling  point.  It  checked  that 
of  o-allyl  anisole.  This  seemed  to  show  conclusively  that  the  com- 
pound was  the  one  desired  and  so  the  work  was  directed  to  a study  of 
this  syrup  with  the  Intention  of  causing  it  to  crystallize  if  possi- 
ble or  of  making  a crystalline  derivative. 


15 


An  attempt  was  made  to  carry  out  the  reaction  in  the  presence  of 
benzene  but  the  only  effect  seemed  to  be  that  of  forming  an  emulsion. 

It  was  next  found  that  the  reaction  was  more  rapid  when  alkali 
was  added  in  accordance  with  the  general  facts  concerning  these  addi- 
tion compounds.  The  method  followed  in  making  this  syrup  in  most  of j 
the  subsequent  runs  was  to  put  together  in  a container  the  substances 
in  molecular  quantities  as  noted  in  the  first  experiment  and  then  to  j 
add  a 10®/©  NaOH  solution  in  small  portions  waiting  each  time  until 
the  basic  mercuric  acetate  had  disappeared  before  adding  another 
portion.  This  was  continued  until  no  precipitate  appeared  on  the 
addition  of  more  alkali  and  the  heavy  syrup  had  settled  to  the  bot- 
tom of  the  container. 

It  was  found  that  the  syrup  solidified  when  chilled  with  ice  but 
melted  again  when  warmed.  This  fact  was  used  in  most  of  the  experi- 
ments to  separata  the  reaction  mixture  from  the  syrup.  It  was 
chilled  and  then  the  water  solution  was  poured  off. 

The  next  efforts  were  directed  toward  the  formation  of  a crystal- 
line iodide  or  nitrate  from  this  syrupy  acetate.  Some  of  the  acetate 
which  had  been  made  as  above  was  treated  with  a concentrated  solution 
of  KI.  After  standing  two  days  a yellow  oil  had  separated  on  top  of 
the  solution.  This  was  separated  and  washed  with  water.  Then  to 
1/2  cc.  of  this  oil  were  added  3 cc.  of  concentrated  HGl  and  upon 
gentle  heating  a red  compound  formed  which  was  soluble  in  excess  KI 
solution  and  gave  a large  amount  of  HgS  when  treated  with  HgS. 
o-Allyl  anlsole  was  also  obtained.  It  would  seem  from  this  experi- 
ment that  the  iodide  derivative  was  also  oily  since  the  red  compound 


16 


must  have  been  merc\iric  iodide  and  the  oil  obtained  must  have  been 
the  mercuric  iodide  derivative* 

An  attempt  was  made  to  make  the  nitrate  but  oxidation  appeared 
to  take  place  and  only  a very  gxirnmy,  tarry  mass  was  obtained. 

It  was  found  that  this  syrup  was  slightly  soluble  in  ether  but 
insoluble  in  petroleum  ether.  Consequently  tlie  following  method  of 
purification  was  carried  out.  The  syrup  made  as  above  was  stirred 
with  fairly  large  amounts  of  ether  several  times  until  most  of  the 
syrup  had  dissolved.  The  ether  solution  was  then  dried  over  sodium 
sulphate  suid  the  ether  was  then  distilled  off  leaving  the  syrup. 
This  was  then  shaken  well  with  boiling  petroleum  ether  to  remove 
any  o-allyl  anlsole  and  then  the  syrup  was  again  taken  up  in  ether, 
dried,  and  the  ether  was  distilled.  This  left  a small  amount  of  a 
heavy,  viscous  oil,  of  about  the  appearance  of  glycerine.  This  oil 
dissolved  almost  Instantly  in  concentrated  HCl  to  give  a mercury 
solution  and  o-allyl  anisole. 

It  was  thou^t  that  this  product  would  be  soluble  in  alcohol  but 
on  the  addition  of  this  solvent  to  some  of  the  syrup  which  had  not 
been  purified  by  ether  extraction,  a large  amount  of  a white  pre- 
cipitate separated  at  once.  This  was  filtered  and  was  found  to  be 
insoluble  in  hot  concentrated  HCl.  It  melted  at  160®-170®  with  de- 
composition, and  burned  with  a smoky  flame  when  heated  in  a porce- 
lain dish  and  ignited.  The  nature  of  this  substance  was  not  deter- 


^ It  was  later  found  that  sodium  sulphate  had  a strong  tendency  to 


absorb  the  syrup 


f 'A 


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17 


mined,  V/ere  it  not  for  its  insolubility  in  HCl,  it  might  be  an 
isomeric  product  and  the  syrup  rai^t  be  a mixture  of  two  substances 
such  as  are  obtained  with  safrol  and  methyl  cavicrol^®.  Its  insolu- 
bility in  HCl  makes  this  hard  to  believe  and  probably  the  white  com- 
pound is  a basic  mercuric  acetate. 

One  portion  of  this  alcohol  solution  was  vacuum  distilled  until 
the  alcohol  was  removed,  but  as  soon  as  it  was  heated  in  an  attempt 
to  distill  the  syrup  which  remained,  it  decomposed  giving  metallic 
mercury.  This  was  carried  out  at  14  mm. 

The  alcohol  was  distilled  from  another  portion  and  a syrup  was 
obtained  similar  in  appearance  to  that  obtained  by  ether  extraction. 
This  was  again  dissolved  in  alcohol  and  a salt  solution  was  added, 

A white,  flocculent  precipitate  came  dovm  at  once  and  was  filtered. 
It  gave  no  sharp  melting  point  but  commenced  to  soften  at  65®  and 
melted  at  70®,  It  was  fo\md  to  be  insoluble  in  all  the  common  sol- 
vents but  dissolved  in  concentrated  HCl  almost  immediately  on  addi- 
tion and  gave  o-allyl  anlsole  and  mercury  in  solution.  This  was 
probably  the  mercuric  chloride  derivative  of  o-allyl  anisole  but  be- 
cause it  could  not  be  crystallized  this  could  not  be  proved.  It  is 
not  known  why  this  product  would  not  dissolve  in  alcohol  as  analo- 
gous products  do. 

The  final  experiment  was  an  attempt  to  carry  out  the  addition  in 
methyl  alcohol  solution.  To  a solution  32  g,  mercxirlc  acetate  in 
200  cc,  methyl  alcohol  were  added  13,3  g,  o-allyl  anlsole  and  the 
solution  was  refluxed  for  ei^t  hoiirs.  There  was  a small  amount  of 
a white  residue  (l/2  gra, ) and  this  was  filtered  off  and  the  alcohol 


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18 


was  vacuum  distilled  leaving  a heavy,  syrupy  oil  very  similar  in  ap- 
pearance to  the  product  obtained  above  -hen  it  had  been  purified  by 
ether  extraction.  Slightly  more  than  a theoretical  yield  for  the 
compound  was  obtained 


but  this  was  probably  due  to  an  error  in  wei^t,  since  the  whole 
flask  was  weired,  or  to  the  occlusion  of  some  alcohol. 

About  half  this  product  was  decomposed  with  concentrated  HCl, 
less  than  a minute  being  required,  and  then  the  diluted  solution 
was  extracted  with  ether,  the  ether  solution  was  dried  over  calciiam 
chloride,  and  the  boiling  point  of  the  residual  oil  was  taken.  It 
boiled  at  198®  and  this  boiling  point  was  checked  with  pure  o-allyl 
anisole  in  the  same  apparatus. 

The  results  of  this  work  are  rather  inconclusive,  d\ae  in  large 
part  to  the  difficulty  of  working  with  these  syrupy  products.  It 
seems  to  be  fairly  clearly  indicated,  however,  that  mercuric  acetate 
reacts  with  o-allyl  anisole  to  give  a syrup  which  probably  by  analogy 
has  the  structure 


and  that  a similar  product  is  formed  in  alcohol  solution  of  the 
probable  structure 


A satiirated  solution  of  mercuric  chloride  containing  a slight  ex- 


OCH3 

CHs  - GH  - GHg  - HgCaHoOa 


OH 

GHg  - GH  - CHa  - HgCaHsOg 


Mercuric  Chloride  and  o-Allyl  Anisole . 


19 


cess  of  HCl  was  treated  with  a small  amount  of  o-allyl  anisole  and 
the  mixture  allowed  to  stand  for  several  days  with  frequent  shaking# 
No  reaction  could  he  detected# 

The  same  experiment  was  tried  with  the  addition  of  alkali  in 
enou^  excess  to  precipitate  basic  merctoric  chloride#  This  time 
after  a days  standing  the  oil  sank  to  the  bottom  and  became  syrupy 
as  in  the  case  of  the  mercuric  acetate  indicating  the  probable  for- 
mation of  a mercupochloro  addition  product# 

Determination  of  the  Time  of  Decomposition  of 
oc -Mercurochloro  Methyl  Coumarane  by  Acids# 

In  these  experiments  the  strength  of  the  acids  used  was  deter- 
mined by  titration  against  a standard  alkali#  Fifty  milligram 
samples  of  -mercurochloro  methyl  coumarane  were  accurately  weigh©<i 
into  small  test  tubes  and  in  each  case  2 cc#  of  the  standard  acid 
was  added  and  the  tube  was  shaken  well#  As  soon  as  the  crystals  ap- 
peared to  have  changed  to  an  oil  the  time  was  taken#  However,  the 
decomposition  was  probably  not  complete  because  in  each  case  it  was 
observed  that  on  longer  standing  the  oil  became  lighter  and  floated 
to  the  top# 


20 


Table* 


Acid  ®/  Composition  Time  for  Decomposi-  Remarks 

® tion  in  Cold  (29®) 


1. 

HCl  .... 

33*46 

• • • • 

2 1/2  min* 

1 

2. 

HCl  .... 

30*00 

• • e e 

4 1/2  min* 

3* 

HCl  .... 

23*80 

• • • • 

9 min* 

4* 

HCl  .... 

14*20 

• • • • 

5 hours 

5* 

HCl  .... 

7*50 

• ♦ • # 

21  1/2  hours 

6* 

HCl  ...  * 

2*50 

• • • • 

No  solution) 

• • a • 

Dissolves 

) 

• • • • 

slowly 

7* 

HCl  .... 

1*30 

• • • • 

No  solution) 

• • • • 

with  heating 

8* 

Acetic  .... 

100 

• • • • 

No  solution) 

• • • • 
• • • • 

On  boiling 

) 

• • e • 

solution  oc- 

9* 

Acetic  .... 

80 

e • • • 

No  solution) 

• • • • 

curred  but 

) 

0 • • • 

on  cooling 

10* 

Acetic  .... 

56 

• • • • 

No  solution) 

• • • # 

-mercuro- 

• • • • 

chloro 

methyl  coiara- 
arane  pre- 
cipitated. 

As  opposed  to  these  figures  the  derivative  of  o-allyl  anisole 

was  decomposed  almost  Instantly  by  concentrated  HCl  (o3.46®/  )•  It 

o 

was  decomposed  by  7.5®/©  HCl  and  gentle  warming  in  five  minutes 
while  under  the  same  conditions  cC  -mercur-ochloro  methyl  coumarane 
required  ten  minutes* 


I 


r 


21 


IV.  CONCLUSION. 

It  is  admitted  that  the  decomposition  of  these  olefine  mercury 
compounds  by  HCl  is  difficult  to  explain  on  the  basis  of  a struc- 
tural formula;  but  it  is  much  more  difficult  to  explain  the  other 
reactions  of  these  compounds  and  particularly  the  formation  of 
this  coumarane  derivative  on  the  basis  of  a molecular  formula.  It 
is  conceivable  that  the  mercury  has  some  sort  of  a loosening  action 
on  the  hydroxyl  group  under  the  influence  of  acids  because  many 
cases  are  now  known  of  one  group's  affecting  another  in  such  a man- 
ner. It  may  be  concluded,  therefore,  that  although  we  are  not  sure 
just  what  the  mechanism  of  the  decomposition  of  these  compounds  by 
HCl  is,  the  structure  as  proposed  by  Sand  is  essentially  correct. 


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22 


V,  SUMMARY. 

1.  The  mercuric  chloride  derivative  of  o-allyl  phenol  has  been 
made  and  it  has  been  shown  that  it  is  a coumarane  derivative  of  the 
structiire 

^ ^ CHg'^CH  - CHa  - HgCl 


2.  It  has  been  shown  that  this  compound  is  formed  with  fairly 
large  yields  in  acid  solution  and  that  it  is  decomposed  with  greater 
difficulty  by  acids  than  other  mercury  olefine  derivatives. 

3.  The  mercuric  acetate  derivative  of  o-allyl  anisole  has  been 
made  but  its  structure  has  not  been  proved  due  to  its  syrupy  nature. 

4.  A new  proof  of  the  structure  of  the  mercury  derivatives  of 
the  olefines  as  proposed  by  Sand  has  been  given. 


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VI.  BIBLIOGRAPHY 


1.  Compt.  rend. 126,  1145-1148  (1898). 

2.  Ber.^,  1340-1353  (1900). 

3.  Ann. 420.  170-190  (1920). 

4.  Ber.M,  1387  (1901). 

5.  Ann. 329,  151  (1903). 

6.  Ber.M,  1385  (1901). 

7.  Ber.44,  1432  (1911). 

8.  Thesis  by  Roman  (1922). 

9.  Ber.^,  3157  (1912);  Ann. 401.  561  (1913). 

10.  J.  Am.  Chem.  Soc .41,  648  (1919). 

11.  Ber.54,  2079  (1921). 

12.  Organic  Compounds  of  Mercury,  p.365. 

13.  Ber.36,  3575  (1903). 


